EP3158101B1 - Duplexedelstahl - Google Patents

Duplexedelstahl Download PDF

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EP3158101B1
EP3158101B1 EP15809637.0A EP15809637A EP3158101B1 EP 3158101 B1 EP3158101 B1 EP 3158101B1 EP 15809637 A EP15809637 A EP 15809637A EP 3158101 B1 EP3158101 B1 EP 3158101B1
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weight
stainless steel
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austenitic stainless
steel according
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EP3158101A1 (de
EP3158101A4 (de
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James Oliver
Jan Y. Jonsson
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Outokumpu Oyj
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Outokumpu Oyj
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/005—Ferrite
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron

Definitions

  • This invention relates to a duplex ferritic austenitic stainless steel which has high formability with the TRIP (Transformation Induced Plasticity) effect and high corrosion resistance and optimized pitting resistance equivalent (PRE).
  • TRIP Transformation Induced Plasticity
  • PRE pitting resistance equivalent
  • the transformation induced plasticity (TRIP) effect refers to the transformation of metastable retained austenite to martensite during plastic deformation as a result of imposed stress or strain. This property allows stainless steels having the TRIP effect to have a high formability, while retaining excellent strength.
  • the EP patent application 2172574 and the JP patent application 2009052115 discolose a ferritic austenitic stainless steel which contains in weight % 0,002 - 0,1 % C, 0,05 - 2 % Si, 0,05 - 5 % Mn, 17 - 25 % Cr, 0,01 - 0,15 % N, optionally less than 5 % Ni, optionally less than 5 % Cu, optionally less than 5 % Mo, optionally less than 0,5 % Nb and optionally less than 0,5 % Ti.
  • the M d temperature is limited to the range -10 °C ⁇ M d ⁇ 110 °C.
  • the pitting resistance equivalent (PRE), which is calculated using the formula PRE %Cr + 3,3* % Mo + 10 * % ⁇ N ⁇ %Mn , is described to be over 18.
  • the Mo content is only optional, and for the calculation of the M d temperature is based on the chemical composition of the austenite phase being only 10 - 50 vol % of the whole microstructure.
  • the EP patent application 1715073 discoses an austenitic ferritic stainless steel containing in weight % less than 0,2 % C, less than 4 % Si, less than 12 % Mn, 15 - 35 % Cr, less than 3 % Ni, 0,05 - 0,6 % N, optionally less than 4 % Cu, optionally less than 4 % Mo, optionally less than 0,5 % V and optionally less than 0,1 % Al.
  • the volume fraction of the austenite phase is in a range from 10 to 85 %, and the amount of (C+N) in the austenite phase is in the range from 0,16 to 2 weight %.
  • the EP patent application 1715073 also has molybdenum (Mo) as an optional element.
  • WO patent application 2011/135170 a method for manufacturing a ferritic-austenitic stainless steel having good formability and high elongation, which steel contains in weight % less than 0,05 % C, 0,2-0,7 % Si, 2-5 % Mn, 19-20,5 % Cr, 0,8-1,35 % Ni, less than 0,6 % Mo, less than 1 % Cu, 0,16-0,24 % N, the balance being iron and inevitable impurities.
  • the stainless steel of the WO patent application 2011/135170 is heat treated so that the microstructure of the stainless steel contains 45 - 75 % austenite in the heat treated condition, the remaining microstructure being ferrite. Further, the measured M d30 temperature of the stainless steel is adjusted between 0 and 50 °C in order to utilize the TRIP effect for improving the formability of the stainless steel.
  • duplex ferritic austenitic stainless steel utilizing the TRIP effect which contains less than 0,04 weight % C, less than 0,7 weight % Si, less than 2,5 weight % Mn, 18,5-22,5 weight % Cr, 0,8-4,5 weight % Ni, 0,6-1,4 weight % Mo, less than 1 weight % Cu, 0,10-0,24 weight % N, the rest being iron and inevitable impurities occurring in stainless steels.
  • Sulphur is limited to less than 0,010 weight % and preferably less than 0,005 weight %
  • the phosphorus content is less than 0,040 weight % and the sum of sulphur and phosphorus (S+P) is less than 0,04 weight %
  • the total oxygen content is below 100 ppm.
  • the duplex stainless steel optionally contains one or more added elements in the following: the aluminium content is maximized to less than 0,04 weight % and preferably the maximum is less than 0,03 weight %.
  • boron, calcium and cerium are optionally added in small quantities; the preferred contents for boron and calcium are less than 0,003 weight % and for cerium less than 0,1 weight %.
  • cobalt can be added up to 1 weight % for a partial replacement to nickel, and tungsten can be added up to 0,5 weight % as partial replacement to molybdenum.
  • one or more of the group containing niobium, titanium and vanadium can be optionally added in the duplex stainless steel of the invention, the contents of niobium and titanium being limited up to 0,1 weight % and the vanadium content being limited up to 0,2 weight %.
  • the pitting resistance equivalent (PRE) has been optimized to give good corrosion resistance, being at the range of 27-29,5.
  • the TRIP (Transformation Induced Plasticity) effect in the austenite phase is maintained in accordance with the measured M d30 temperature at the range of 0-90 °C, preferably at the range of 10-70 °C, in order to ensure the good formability.
  • the proportion of the austenite phase in the microstructure of the duplex stainless steel of the invention is in the heat treated condition 45-75 volume %, advantageously 55-65 volume %, the rest being ferrite, in order to create favourable conditions for the TRIP effect.
  • the heat treatment can be carried out using different heat treatment methods, such as solution annealing, high-frequency induction annealing or local annealing, at the temperature range from 900 to 1200 °C, preferably from 950 to 1150 °C.
  • JPH 03082739 discloses a duplex stainless steel excellent in hot workability and corrosion resistance.
  • the object of the present invention is to improve the properties of the duplex stainless steels described in the prior art and to achieve a new duplex ferritic austenitic stainless steel utilizing the TRIP effect with high pitting resistance equivalent (PRE) and giving therefore superior corrosion resistance.
  • PRE pitting resistance equivalent
  • the duplex ferritic austenitic stainless steel contains less than 0,04 weight % C, 0,2 - 0,8 weight % Si, 0,3 - 2,0 weight % Mn, 14,0 - 19,0 weight % Cr, 2,0 - 5,0 weight % Ni, 4,0 - 7,0 weight % Mo, less than 4,5 weight % W, 0,1 - 1,5 weight % Cu, 0,14 - 0,23 weight % N, the rest being iron and inevitable impurities occurring in stainless steels.
  • Sulphur is limited to less than 0,010 weight % and preferably less than 0,005 weight %, the phosphorus content is less than 0,040 weight % and the sum of sulphur and phosphorus (S+P) is less than 0,04 weight %, and the total oxygen content is below 100 ppm.
  • the duplex stainless steel of the invention optionally contains one or more added elements in the following: the aluminium content is maximized to less than 0,04 weight % and preferably the maximum is less than 0,03 weight %. Further, boron, calcium, cerium and magnesium are optionally added in small quantities; the preferred contents for boron and calcium are less than 0,004 weight %. for cerium less than 0,1 weight % and for magnesium less than 0,05 weight %. Optionally cobalt can be added up to 1 weight % for a partial replacement to nickel.
  • one or more of the group containing niobium, titanium and vanadium can be optionally added in the duplex stainless steel of the invention, the contents of niobium and titanium being limited up to 0,1 weight % and the vanadium content being limited up to 0,2 weight %.
  • the pitting resistance equivalent has been optimized to give good corrosion resistance, being at the range of 35 - 42.
  • the TRIP (Transformation Induced Plasticity) effect in the austenite phase is maintained in accordance with the measured M d30 temperature at the range of -30 - +90 °C, preferably at the range of 0 - +60 °C, in order to ensure the good formability.
  • the M d30 -temperature which is a measure for the austenite stability to the TRIP effect, is defined as the temperature at which 0,3 true strain yields 50% transformation of the austenite to martensite.
  • the proportion of the austenite phase in the microstructure of the duplex stainless steel of the invention is in the heat treated condition 50 - 80 volume %, advantageously 55 - 70 volume %, the rest being ferrite, in order to create favourable conditions for the TRIP effect.
  • the heat treatment can be carried out using different heat treatment methods, such as solution annealing, high-frequency induction annealing, local annealing, or any other type of heat treatment at the temperature range from 900 to 1200 °C, preferably from 950 to 1150 °C.
  • the sum of chromium, molybdenum and optional tungsten with the formula Cr+Mo+0,5W is critical to maintain the M d30 temperature in the desired range in order to ensure good formability.
  • Carbon (C) partitions to the austenite phase and has a strong effect on austenite stability. Carbon can be added up to 0,04 % but higher levels have detrimental influence on corrosion resistance.
  • Nitrogen (N) is an important austenite stabilizer in duplex stainless steels and like carbon it increases the stability against martensite. Nitrogen also increases strength, strain hardening and corrosion resistance. The general empirical expressions on the M d30 temperature indicate that nitrogen and carbon have the same strong influence on austenite stability. Because nitrogen can be added to stainless steels in larger extent than carbon without adverse effects on corrosion resistance the nitrogen contents from 0,14 to 0,23 % are effective in present stainless steels.
  • Silicon (Si) is normally added to stainless steels for deoxidizing purposes in the melt shop and should not be below 0,2 %. Silicon stabilizes the ferrite phase in duplex stainless steels but has a stronger stabilizing effect on austenite stability against martensite formation than shown in current expressions. For this reason silicon is maximized to 0,8 %, preferably to 0,5 %.
  • Manganese (Mn) is an important addition to stabilize the austenite phase and to increase the solubility of nitrogen in the stainless steel. Manganese can partly replace the expensive nickel and bring the stainless steel to the right phase balance. Too high level in the content will reduce the corrosion resistance. Manganese has a stronger effect on austenite stability against deformation martensite and, therefore, the manganese content must be carefully addressed.
  • the range of manganese shall be 0,3 - 2,0 %.
  • Chromium is the main addition to make the steel resistant to corrosion. Being ferrite stabilizer chromium is also the main addition to create a proper phase balance between the austenite phase and the ferrite phase. In addition, and together with molybdenum, chromium strongly increases the resistance to martensite formation. In order to provide a high PRE whilst maintaining an optimal TRIP effect, the range of chromium is limited to 14,0 % - 19,0 % thanks to the increase in the molybdenum content. Preferably the chromium content is 14,0 - 18,0 %.
  • Nickel (Ni) is an essential alloying element for stabilizing the austenite phase and for good ductility and at least 2,0 % must be added to the stainless steel of the invention. Having a large influence on austenite stability against martensite formation nickel has to be present in a narrow range. Further, because of nickel's high cost and price fluctuation nickel should be maximized in the stainless steel of the invention to 5,0 %.
  • Copper (Cu) is normally present as a residual of 0,1 - 0,5 % in most stainless steels, when the raw materials to a great deal are in the form of stainless scrap containing this element. Copper is a weak stabilizer of the austenite phase but has a strong effect on the resistance to martensite formation and must be considered in evaluation of formability of the present stainless steels.
  • the copper additions can also increase the resistance to sigma phase. An intentional addition up to the range 0,1 - 1,5 % can be made, but preferably the copper content is in the range 0,1 - 0,7 %, more preferably in the range 0,1 - 0,5 %.
  • Molybdenum is a ferrite stabilizer that can be added to strongly increase the corrosion resistance and, therefore, molybdenum shall have a content at least 4,0 % in order to achieve the high PRE. Further, molybdenum, like chromium, strongly increases the resistance to martensite formation and reduces the TRIP effect. Therefore, molybdenum is added to the stainless steel of the invention to counter balance the effect of chromium in terms of TRIP and PRE. For this purpose molybdenum should be maximised to 7.0 %, preferably 6,5%.
  • Tungsten (W) has similar properties as molybdenum and can sometimes replace molybdenum.
  • tungsten and molybdenum promote sigma phase precipitation and the sum of the molybdenum and tungsten contents according to the formula (Mo + 0,5W) should be less than 7,0 %, preferably 4,0 - 6,6 %, where the promotion of sigma and chi phases are possible to handle in technically relevant processes.
  • the most important influence of tungsten is the surprisingly positive impact on the TRIP effect which in turn could be related to the effect on the stacking fault energy of the alloy since the stacking fault energy controls the deformation response in terms of dislocation glide, twinning or martensite formation.
  • tungsten should be limited up to 3,5 %, but preferably at least 0,5 % when tungsten is used to replace molybdenum.
  • the co-effect of the chromium, molybdenum and optional tungsten contents in weight % is in the range of 20 ⁇ (Cr+Mo+0,5W) ⁇ 23,5 where the ratio Cr/(Mo+0,5W) is in the range of 2 - 4,75.
  • Boron (B), calcium (Ca) and cerium (Ce) are added in small quantities in duplex steels to improve hot workability and not at too high contents as this can deteriorate other properties.
  • the preferred contents for boron and calcium in the stainless steel of the invention are less than 0,004 % and for cerium less than 0,1 %.
  • Magnesium (Mg) is a strong oxide and sulphide former. When added as a final steelmaking step it forms magnesium sulphide (MgS) and transforms a potential low melting sulphide eutectic phase to a more stable morphology with a higher melting temperature thus improving the hot ductility of the alloy.
  • the magnesium content is limited to less than 0,05 %.
  • Sulphur (S) in duplex steels deteriorates hot workability and can form sulphide inclusions that influence pitting corrosion resistance negatively.
  • the content of sulphur should therefore be limited to less than 0,010 % and preferably less than 0,005 %.
  • Phosphorus (P) deteriorates hot workability and can form phosphide particles or films that influence corrosion resistance negatively.
  • the content of phosphorus should therefore be limited to less than 0,040 %, and so that the sum of sulphur and phosphorus (S+P) contents is less than 0,04 %.
  • Oxygen (O) together with other residual elements has an adverse effect on hot ductility.
  • the presence of oxide inclusions may reduce corrosion resistance (pitting corrosion) depending on type of inclusion.
  • High oxygen content also reduces impact toughness.
  • sulphur oxygen improves weld penetration by changing the surface energy of the weld pool.
  • the advisable maximum oxygen level is below 100 ppm. In a case of a metallic powder the maximum oxygen content can be up to 250 ppm.
  • Aluminium (Al) should be kept at a low level in the duplex stainless steel of the invention with high nitrogen content as these two elements can combine and form aluminium nitrides that will deteriorate the impact toughness.
  • the aluminium content is limited to less than 0,04 % and preferably to less than 0,03 %.
  • Co has similar metallurgical behaviour as its sister element, nickel, and cobalt may be treated in much the same way in steel and alloy production. Cobalt inhibits grain growth at elevated temperatures and considerably improves the retention of hardness and hot strength. Cobalt increases the cavitation erosion resistance and the strain hardening. Cobalt reduces the risk of sigma phase formation in super duplex stainless steels. The cobalt content is limited up to 1,0 %.
  • titanium (Ti), vanadium (V) and niobium (Nb) belong to a group of additions so named because they significantly change the steels properties at low concentrations, often with beneficial effects in carbon steel but in the case of duplex stainless steels they also contribute to undesired property changes, such as reduced impact properties, higher surface defects levels and reduced ductility during casting and hot rolling. Many of these effects depend on their strong affinity for carbon and in particular nitrogen in the case of modern duplex stainless steels.
  • niobium and titanium should be limited to maximum level of 0,1%, whereas vanadium is less detrimental and should be less than 0,2%.
  • the table 1 contains also the chemical composition for the reference duplex stainless steel of commonly known as 2205 (Q) and the reference duplex stainless steels of the WO patent application 2011/135170 named as R and the WO patent application 2013/034804 named as S, all the contents of the table 1 in weight %.
  • the alloys A - P were manufactured in a vacuum induction furnace in 1 kg laboratory scale to small slabs that were forged and cold rolled down to 1,5 mm thickness.
  • the referred alloys Q to S were produced in 100 ton production scale followed by hot rolling and cold rolling to coil form with varying final dimensions.
  • the actual measured M d30 temperatures (M d30 measured) of the table 2 were established by straining the tensile samples to 0,30 true strain at different temperatures and by measuring the fraction of the transformed martensite with Satmagan equipment. Satmagan is a magnetic balance in which the fraction of ferromagnetic phase is determined by placing a sample in a saturating magnetic field and by comparing the magnetic and gravitational forces induced by the sample.
  • the calculated M d30 temperatures (M d30 calc) in the table 2 were achieved in accordance with a mathematical constraint of optimization.
  • the sums of the element contents for C+N, Cr+Si, Cu+Mo+0,5W, Mn+Ni and Cr+Mo+0,5W in weight % are also calculated for the alloys of the table 1 in the table 2.
  • the sums C+N and Mn+Ni represent austenite stabilizers, while the sum Si+Cr represents ferrite stabilizers and the sum Cu+Mo+0,5W elements having resistance to martensite formation.
  • the sum formula Cr+Mo+0,5W is critical to maintain the M d30 temperature in the optimal range in order to ensure the good formality.
  • Alloys C, D, G, I, N, O, P, Q, R and S are outside the range of the present invention.
  • the PRE value having the range of 35 - 42 is much higher than the PRE value in the referred duplex stainless steels R and S which means that the corrosion resistance of the alloys A - P is higher.
  • the PRE is of the same level or slightly higher than the reference alloy Q.
  • the predicted M d30 temperatures using the Nohara expression (1) are essentially different from the measured M d30 temperatures for the alloys on the table 2. Further, from the table 2 it is noticed that the calculated M d30 temperatures agree well with the measured M d30 temperatures, and the mathematical constraint of optimization used for the calculation is thus very suitable for the duplex stainless steels of the invention.
  • a chemical composition window for Si+Cr and Cu+Mo+0,5W is established with the preferred ranges of 0,14 - 0,27 for C+N and 2,3 - 7,0 for Mn+Ni when the duplex stainless steel of the invention was annealed at the temperature of 1050 °C. It is also noticed in Fig. 1 that the sum Si+Cr is limited to 14,2 ⁇ (Si+Cr) ⁇ 19,80 in accordance with the stainless steel of the invention.
  • the chemical composition window which lies within the frame of the area a', b', c', d', e and f' in Fig. 1 , is defined with the following labelled positions of the coordination in the table 3.
  • Table 3 Si+Cr % Cu+Mo+0,5W % C+N % Mn+Ni % a' 19,80 4.11 0,14 2,30 b' 19.8 4.29 0,14 2,30 c' 17.27 6,90 0,14 2,30 d' 14.20 7.86 0,27 7,00 e' 14.20 6.66 0,27 7,00 f' 15.32 5,50 0,27 7,00
  • Fig. 2 illustrates one chemical composition example window of Fig. 1 when constant values of 0,221 for C+N and 3,90 for Mn+Ni are used at all points instead of the ranges for C+N and Mn+Ni in Fig. 1 .
  • the same minimum limitations are given to the sum of Si+Cr in Fig. 2 as in Fig. 1 .
  • the chemical composition window which lies within the frame of the area a, b, c, d and e, in Fig. 2 , is defined with the following labelled positions of the coordination in the table 4.
  • Fig. 3 illustrates a chemical composition window for C+N and Mn+Ni with the preferred composition ranges 14,2 - 18,7 for Cr+Si and 4,1 - 9,5 for Cu+Mo+0,5W, when the duplex stainless steel was annealed at the temperature of 1050 °C. Further, in accordance with invention the sum C+N is limited to 0,14 ⁇ (C+N) ⁇ 0,27 and the sum Mn+Ni is limited to 2,3 ⁇ (Mn+Ni) ⁇ 7,0.
  • the chemical composition window which lies within the frame of the area p', q' r' and s' in Fig. 3 , is defined with the following labelled positions of the coordination in the table 5.
  • Fig. 4 illustrates one chemical composition example window of Fig. 3 with the constant values of 17,3 for Cr+Si and 5,3 for Cu+Mo and further, with the limitations of (C+N) ⁇ 0,27 and (Mn+Ni)>2,3.
  • the chemical composition window which lies within the frame of the area p, q, r, s and t in Fig. 4 , is defined with the following labelled positions of the coordination in the table 6.
  • the alloys of the present invention A - P as well as the reference materials Q, R and S above were further tested by determining the yield strengths R p0.2 and R p1.0 and the tensile strength R m as well as the elongation values for A 50 , A 5 and A g in the longitudinal direction where A g is the uniform elongation or elongation to plastic instability.
  • the table 7 contains the results of the tests for the alloys A - P of the invention as well as the respective values for the reference duplex stainless steels C, D, G, I, N, O, P, Q, R and S.
  • the results in the table 7 show that the yield strength values R p0.2 and R p1.0 for the alloys A - P are lower than the respective values for the reference duplex stainless steels Q, R and S and the tensile strength value R m is similar to the reference duplex stainless steels Q, R and S.
  • the elongation values A 50 , A 5 and A g of the alloys A - P are higher than the reference alloy Q with a similar PRE. Because the alloys A - P according to the invention are manufactured in the laboratory scale and the reference duplex stainless steels Q, R and S are produced in the production scale, the strength values of the table 7 are not directly comparable with each other.
  • n-values of the alloys A-P are all higher than the reference alloy Q indicating the importance of the TRIP effect for the work hardening rate. Compared to the reference alloys R and S the n(10-15 %) values are somewhat higher while the n(15-20%) values are considerably higher indicating the optimized work hardening rate for the alloys A-P of the present invention utilizing the TRIP effect.
  • duplex ferritic austenitic stainless steel of the invention can be produced as ingots, slabs, blooms, billets and flat products such as plates, sheets, strips, coils, and long products such as bars, rods, wires, profiles and shapes, seamless and welded tubes and/or pipes. Further, additional products such as metallic powder, formed shapes and profiles can be produced.

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Claims (13)

  1. Duplex ferretisch-austenitischer Edelstahl, der eine hohe Formbarkeit aufgrund des TRIP-Effekts und eine hohe Korrosionsbeständigkeit mit dem Äquivalent der hohen Lochfraßbeständigkeit aufweist, dadurch gekennzeichnet, dass der Duplex-Edelstahl weniger als 0,04 Gew.-% Kohlenstoff, 0,2 bis 0,8 Gew.-% Silizium, 0,3 bis 2,0 Gew.-% Mangan, 14,0 bis 19,0 Gew.-% Chrom, 2,0 bis 5,0 Gew.-% Nickel, 4,0 bis 7,0 Gew.-% Molybdän, weniger als 4,5 Gew.-% Wolfram, 0,1 bis 1,5 Gew.-% Kupfer, 0,14 bis 0,23 Gew.-% Stickstoff, und wahlweise ein oder mehrere hinzugefügte Elemente enthält: weniger als 0,04 Gew.-% Al, weniger als 0,004 Gew.-% B, weniger als 0,004 Gew.-% Ca, weniger als 0,1 Gew.-% Ce, bis zu 1 Gew.-% Co, bis zu 0,1 Gew.-% Nb, bis zu 0,1 Gew.-% Ti, bis zu 0,2 Gew.-% V, der Rest ist Eisen und unvermeidliche Verunreinigungen, weniger als 0,010 Gew.-%, vorzugsweise weniger als 0,005 Gew.-% S, weniger als 0,040 Gew.-% P, sodass die Summe (S + P) weniger als 0,04 Gew.-% beträgt, und der gesamte Sauerstoffgehalt, der in Edelstählen vorkommt, unter 100 ppm liegt, und sodass der Co-Effekt der Chrom-, Molybdän- und Wolframanteile in Gew.-% im Bereich von 20 < (Cr + Mo + 0,5 W) < 23,5 liegt, wobei das Verhältnis von Cr / (Mo + 0,5 W) im Bereich von 2 bis 4,75 liegt, und der Wert des Lochfraßbeständigkeitsäquivalents (PREN) im Bereich von 35 bis 42 liegt, die Md30-Temperatur liegt im Bereich von (-30 °C) bis (+90 °C), wobei die Formeln PREN = %Cr + 3,3 * (%Mo + 0,5 % W) + 30 * %N - %Mn und Md30 = 551 - 462 (C + N) - 9,2 Si - 8,1 Mn - 13,7 Cr - 29(Ni + Cu) - 18,5 Mo - 68 Nb bei einem Glühen bei einer Temperatur von 1050 °C zutreffen.
  2. Duplex ferretisch-austenitischer Edelstahl nach Anspruch 1, dadurch gekennzeichnet, dass der Anteil der Austenitphase in der Mikrostruktur nach der Wärmebehandlung bei einem Temperaturbereich von 900 bis 1200 °C, vorzugsweise 950 bis 1150 °C 50 bis 80 Vol.-%, vorteilhafterweise 55 bis 75 Vol.-% beträgt, der Rest ist Ferrit.
  3. Duplex ferretisch-austenitischer Edelstahl nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die gemessene Temperatur Md30 im Bereich von 0 °C bis (+60 °C) liegt.
  4. Duplex ferretisch-austenitischer Edelstahl nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Dehnung Ag für die Legierungen größer als 19 % ist, vorzugsweise größer als 25 %.
  5. Duplex ferretisch-austenitischer Edelstahl nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Kaltumformungsrate für die Legierungen dadurch beschrieben wird, dass der n-Wert des Kaltverfestigungsexponenten größer als 0,2 bei ε = 10 bis 15 % ist.
  6. Duplex ferretisch-austenitischer Edelstahl nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Chromanteil 14,0 bis 18,0 Gew.-% beträgt.
  7. Duplex ferretisch-austenitischer Edelstahl nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Kupferanteil 0,1 bis 0,7 Gew.-%, vorzugsweise 0,1 bis 0,5 Gew.-% beträgt.
  8. Duplex ferretisch-austenitischer Edelstahl nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Molybdänanteil 4,0 bis 6,5 Gew.-% beträgt.
  9. Duplex ferretisch-austenitischer Edelstahl nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Wolframanteil weniger als 3,0 Gew.-% beträgt.
  10. Duplex ferretisch-austenitischer Edelstahl nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Summe der Molybdän- (Mo) und Wolframanteile (W) gemäß der Formel (Mo + 0,5 W) weniger als 7,0 Gew.-%, vorzugsweise 4,0 bis 6,6 Gew.-% beträgt.
  11. Duplex ferretisch-austenitischer Edelstahl nach Anspruch 1, dadurch gekennzeichnet, dass das Fenster der chemischen Zusammensetzung, das im Rahmen des Bereichs a', b', c', d', e' und f' in Fig. 1 liegt, durch die folgenden markierten Positionen der Koordination in Gew.-% definiert ist Si+Cr % Cu+Mo + 0,5 W % C+N % Mn+Ni % a' 19,80 4,11 0,14 2,30 b' 19,80 4,29 0,14 2,30 c' 17,27 6, 90 0,14 2,30 d' 14,20 7,86 0,27 7,00 e' 14,20 6, 66 0,27 7,00 f' 15,32 5,50 0,27 7,00
  12. Duplex ferretisch-austenitischer Edelstahl nach Anspruch 1, dadurch gekennzeichnet, dass das Fenster der chemischen Zusammensetzung, das im Rahmen des Bereichs p', q', r' und s' in Fig. 3 liegt, durch die folgenden markierten Positionen der Koordination in Gew.-% definiert ist Si+Cr % Cu+Mo + 0,5 W % C+N % Mn+Ni % p' 18,00 5,00 0,27 7,00 q' 16,00 5,30 0,14 7,00 r' 14,20 7,00 0,14 2,30 s' 17,30 6,80 0,27 2,30
  13. Verwendung von duplex ferretisch-austenitischem Edelstahl nach Anspruch 1, dadurch gekennzeichnet, dass der Stahl als Barren, Brammen, Blöcke, Knüppel, Platten, Bleche, Bänder, Spulen, Stangen, Stäbe, Drähte, Profile und Formen, nahtlose und geschweißte Rohre und/oder Rohrleitungen, Metallpulver, gebildete Formen und Profile hergestellt wird.
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Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107881413B (zh) * 2017-10-18 2019-06-11 江苏理工学院 一种抗菌双相不锈钢及其加工工艺
EP3858684A1 (de) * 2020-01-28 2021-08-04 Outokumpu Oyj Aufgeweitetes rohr für eine kraftfahrzeug-crashbox und zugehöriges herstellungsverfahren
EP3960881A1 (de) * 2020-09-01 2022-03-02 Outokumpu Oyj Austenitischer edelstahl
US20240026509A1 (en) * 2022-07-22 2024-01-25 Carpenter Technology Corporation High molybdenum duplex stainless steel

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1242095A (en) * 1984-02-07 1988-09-20 Akira Yoshitake Ferritic-austenitic duplex stainless steel
US4721600A (en) * 1985-03-28 1988-01-26 Sumitomo Metal Industries, Ltd. Superplastic ferrous duplex-phase alloy and a hot working method therefor
JPH01246343A (ja) * 1988-03-25 1989-10-02 Daido Steel Co Ltd ステンレス鋼
JPH0382739A (ja) * 1989-08-25 1991-04-08 Sumitomo Metal Ind Ltd 熱間加工性と耐食性に優る２相ステンレス鋼
JP2952929B2 (ja) 1990-02-02 1999-09-27 住友金属工業株式会社 ２相ステンレス鋼およびその鋼材の製造方法
JP3270498B2 (ja) * 1991-11-06 2002-04-02 株式会社クボタ 耐割れ性及び耐食性にすぐれる二相ステンレス鋼
JPH10102206A (ja) 1996-09-27 1998-04-21 Kubota Corp 高耐食・高腐食疲労強度二相ステンレス鋼
JP2000313940A (ja) 1999-04-27 2000-11-14 Sumitomo Metal Ind Ltd 二相ステンレス鋼材およびその製造方法
US6551420B1 (en) * 2001-10-16 2003-04-22 Ati Properties, Inc. Duplex stainless steel
EP2280089B1 (de) 2001-10-30 2016-08-10 ATI Properties, Inc. Duplex rostfreier Stahl
US7396421B2 (en) * 2003-08-07 2008-07-08 Sumitomo Metal Industries, Ltd. Duplex stainless steel and manufacturing method thereof
AU2004262702B2 (en) 2003-08-07 2007-05-03 Nippon Steel Corporation Duplex stainless steel and method for production thereof
KR20090005252A (ko) 2004-01-29 2009-01-12 제이에프이 스틸 가부시키가이샤 오스테나이트·페라이트계 스테인레스 강
JP4760031B2 (ja) * 2004-01-29 2011-08-31 Ｊｆｅスチール株式会社 成形性に優れるオーステナイト・フェライト系ステンレス鋼
CN100482843C (zh) 2006-12-31 2009-04-29 许季祥 高性能耐腐蚀稀土超强双相不锈钢及其冶炼工艺
JP4949124B2 (ja) * 2007-05-22 2012-06-06 新日鐵住金ステンレス株式会社 形状凍結性に優れた高強度複相ステンレス鋼板及びその製造方法
KR101253326B1 (ko) * 2007-08-02 2013-04-11 닛폰 스틸 앤드 스미킨 스테인레스 스틸 코포레이션 내식성과 가공성이 우수한 페라이트·오스테나이트계 스테인리스 강 및 그 제조 방법
JP5156293B2 (ja) * 2007-08-02 2013-03-06 新日鐵住金ステンレス株式会社 耐食性と加工性に優れたフェライト・オーステナイト系ステンレス鋼およびその製造方法
JP5213386B2 (ja) * 2007-08-29 2013-06-19 新日鐵住金ステンレス株式会社 成形性に優れたフェライト・オーステナイト系ステンレス鋼薄板及びその製造方法
JP5656432B2 (ja) * 2010-02-12 2015-01-21 新日鐵住金ステンレス株式会社 プレス成形性に優れたフェライト・オーステナイト系ステンレス鋼板およびその製造方法
FI122657B (fi) 2010-04-29 2012-05-15 Outokumpu Oy Menetelmä korkean muokattavuuden omaavan ferriittis-austeniittisen ruostumattoman teräksen valmistamiseksi ja hyödyntämiseksi
DE102010026808B4 (de) * 2010-07-10 2013-02-07 Technische Universität Bergakademie Freiberg Korrosionsbeständiger austenithaltiger phosphorlegierter Stahlguss mit TRIP- bzw. TWIP-Eigenschaften und seine Verwendung
FI126574B (fi) 2011-09-07 2017-02-28 Outokumpu Oy Dupleksinen ruostumaton teräs
JP6405078B2 (ja) 2012-05-07 2018-10-17 株式会社神戸製鋼所 二相ステンレス鋼材および二相ステンレス鋼管
CN103205653A (zh) * 2013-03-27 2013-07-17 宝钢不锈钢有限公司 一种具有优异热塑性和耐蚀性的双相不锈钢及其制造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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